Photofinishers that use photosensitive paper to produce color prints desire short processing times in order to increase output. One way of obtaining rapid processing is to accelerate the development time by increasing the chloride content of the emulsions used in the photographic paper. However, as the chloride content of a photographic emulsion is increased, it becomes more difficult to obtain good invariant photosensitivity.
One of the problems with silver chloride emulsions is their severe propensity to storage deterioration. Photographic emulsions that have a high silver chloride content are prone to fog increase due to high temperature and humidity during storage. These changes may vary from layer to layer resulting in color imbalance and a loss of quality of the print material. Attempts have been made to reduce fog formation during storage by addition of inhibitory agents to the silver halide emulsions. For example, U.S. Pat. Nos. T866,036; 2,440,110; 3,043,696; 3,057,725; 3,226,232; 3,397,986; 3,447,925; and 3,761,277 describe the addition of organic disulfides to silver halide emulsions to lessen the tendency towards fog growth.
High chloride content color print paper also has an undesirable sensitivity to temperature changes during exposure. For example, when the temperature upon exposure rises due to heat from the exposing element during printing, the print density changes if the printing conditions are left at the initial set values. This may result in prints varying in density that were exposed at the normal temperature. Very often, an increase in temperature during exposure of the paper may result in a selective increase in speed in one layer, for instance the cyan layer, over another light sensitive layer such as the magenta layer. This results in improper color balance of the color print, and requires the photofinisher to readjust his printing conditions in order to compensate for this density fluctuation. This results in a loss in operating efficiency.
This deficiency in the use of high silver chloride color paper material is recognized in the art. In particular, EP 0 367,227 (1988) discusses reducing heat sensitivity by employing certain spectral sensitizing dyes in combination with mercapto azoles. However, these dye structures have not proved to be entirely satisfactory in terms of minimizing thermal sensitivity while still maintaining optimal sensitization efficiency. EP 0 325,235 describes using iron ion donating compounds in high chloride photographic elements to reduce their change in sensitivity due to exposure at elevated temperature. Despite these attempts to address the thermal problem, no solution has been found which completely eliminates the above concerns.
U.S. Pat. No. 5,043,259 describes using alkyl and aryl disulfinates in the formation of pre-fogged direct positive silver halide emulsions. U.S. Pat. No. 4,939,072 describes using sulfinates as storage stability improving compounds in color photographs. U.S. Pat. 4,770,987 describes using sulfinates as anti-staining agents along with a magenta coupler in silver halide materials. EP 0 463,639, describes using sulfinic acid derivatives as dye stabilizers. U.S. Pat. No. 4,410,619 describes using a sulfinic acid salt to treat a paper base to prevent discoloration of the photographic material. U.S. Pat. No. 3,466,173 describes using aromatic sulfinates as stabilizers in a direct positive photographic material. EP 0 267,483 describes adding sulfinates during the sensitization of silver bromide emulsions. Similarly, GB 1,308,938 describes using sulfinates during processing of a silver halide photographic material to minimize discoloration of the image tone. U.S. Pat. No. 2,057,764 describes sulfinates as having fog reducing properties.
U.S. Pat. No. 5,110,719 describes using the combination of thiosulfonates with sulfinates and nucleating agents in a direct positive internal latent image core/shell chlorobromide emulsion. U.S. Pat. No. 3,615,534 describes using a combination of iodate ions and sulfinates to prevent yellow fog in silver halide materials. WO 92/12,462 describes using thiosulfonates and sulfinates in controlling speed increase on incubation of color photographic materials. JP 3,208,041 describes using the combination of thiosulfonates with sulfinates in the sensitization of chloride emulsions for color paper. U.S. Pat. No. 2,440,206 describes using the combination of sulfinates along with small amounts of polythionic acids to stabilize photographic emulsions against fog growth. U.S. Pat. No. 2,440,110 describes using the combination of sulfinates with aromatic or heterocyclic polysulfides in controlling fog growth. U.S. Pat. No. 2,394,198 describes using sulfinates with thiosulfonates in stabilizing silver halide emulsions. The use of sulfinates has been described as reducing stain in photographic paper when used in combination with sulfonates in U.S. Statutory Invention Registration H706, and in EP 0 305,926.
U.S. Pat. No. 4,960,689 describes using thiosulfonates in the finish in high Cl emulsions. Aromatic dithiosulfonic acids are described in U.S. Pat. No. 5,009,992 as supersensitizers in an IR-sensitive high Cl emulsion. U.S. Pat. No. 5,079,138; U.S. Pat. No. 5,016,614; EP 0 368,304; EP 0 369,491 and EP 0 371,338 describe using dithiosulfonate to control reduction sensitization in tabular emulsions. EP 0 434,012 and EP 0 435,270 describe using dithiosulfonates during grain formation.
It is well known in the chemical literature that thiosulfonate salts are unstable when dissolved in aqueous solutions. The fact that they decompose into elemental sulfur and sulfinates has been established (A. Westley and J. Westley, Anal. Biochem. 1984, 142, 163-166). This reaction is facile and, generally, a cloudy solution is visible within a short time of the dissolution of the thiosulfonate. Therefore, unless the entire solution of the thiosulfonate is used instantaneously, any unused solution will have to be discarded. This leads to waste and increased cost of producing the photographic material. Additionally, because the product of decomposition, elemental sulfur, is known to be photographically active (see EP 0 447,105; EP 0 297,804; EP 0 294,149 (AgCl); EP 0 327,272; EP 0 349,286; JP 2,161,423; JP 2,148,033; JP 2,148,031; JP 2,146,036; JP 2,033,141; JP 2,020,857; JP 2,301,744; JP 1,196,050; JP 1,196,034; DE 3,902,711; and U.S. Pat. No. 4,962,016), the presence of even a trace of elemental sulfur will cause unexpected and perhaps unwanted photographic responses. The instability of thiosulfonates has led to variability in the sensitized goods as well as increased cost in manufacturing the photographic materials. Thus there exists a need to overcome the disadvantage of the thiosulfonate salts in the process of manufacturing photographic materials containing such salts.
Compounds with labile sulfur moieties have been extensively used as sensitizers of silver halide emulsions. Their use and mechanism of action have been discussed in the photographic art such as by Pouradier, J. Properties of Gelatin in Relation to Its Use in the Preparation of Photographic Emulsions; James, T. H. Ed.; The Theory of the Photographic Process, 4th ed.; Macmillan: New York, 1977, Chapter 2; by Duffin, G. F. Photographic Emulsion Chemistry; Focal: London, 1966, Chapter 2 and by Mueller, F. W. H. in The Photographic Emulsion, Sturge, J. M. Ed.; Neblette's Handbook of Photographic and Reprography, 7th ed.; Van Nostrand Reinhold: New York, 1977, Chapter 2. Common among these labile sulfur compounds are thionates, thioureas, thiosulfates, isothiocyanates and sulfur containing amino acids such as cystine.
Thiatriazoles have been used as supersensitizers for silver halide photographic materials as described in U.S. Pat. No. 4,914,015 (substituted thia and oxa thiatriazoles in red and infrared spectrally sensitized emulsions); U.S. Pat. No. 4,780,404 (amino thiatriazoles); EP 0 447,647 (arylaminothiatriazoles substituted with at least one electron-withdrawing group); and JP 3,033,842 and JP 3,041,438, (thiatriazoles as supersensitizers in red sensitized silver halide emulsions). JP 63/037,348 describes using thiatriazoles in silver chloride emulsions to obtain a low D-min photographic material. JP 63/044,650 and JP 63/037,349 describe a high storage stability material. U.S. Pat. No. 5,070,008 describes using thiatriazoles in silver chloride emulsions with iridium and acidic conditions for formation of AgCl grains. JP 80/142,331 describes using a thiatriazole in a photothermographic paper to reduce fog. U.S. Pat. No. 5,006,448 describes using a thiatriazole as an inhibitor fragment that is released for improving interimage effects.
Pyrazolopentathiepins have been described as fungicides or as sulfur sensitizers in photographic emulsions in EP 0 138,622. In J62/299,963 thiepin is mentioned as an example of a class of compounds used for the preparation of silver halide emulsions which comprises at least 50 mol % of silver bromide.
U.S. Pat. No. 2,385,762 describes using a combination of diamino polysulfides and sulfinates or seleninates to stabilize silver halide emulsions. U.S. application Ser. No. 07/890,884 describes using diamino disulfides and monosulfinates to reduce the thermal sensitivity of high chlorides emulsions. U.S. Pat. No. 4,620,205 discloses the use of dithiodialkylamines as decolorizing agents in a two-color thermosensitive recording material. In JP 54/069,428 and JP 55/144,236 dithiodialkylamines are alleged to sensitize silver bromide emulsions.
There remains a continuing need for an effective means for heat stabilizing high chloride emulsions against thermal changes.